Oligomerizing alpha-olefins with a heterogeneous catalyst

Abstract

An alpha-olefin is oligomerized in the presence of a three-component catalyst comprising a particulate solid adsorbent having boron trifluoride and water adsorbed on the solid adsorbent. For example, 1-decene is oligomerized to a product predominating in the trimer and tetramer using silica as the solid adsorbent.

We claim: 
     
       1. The process for oligomerizing an alpha-olefin having from three to twelve carbon atoms and mixtures thereof with a heterogeneous catalyst which comprises contacting said alpha-olefin in a reactor at a temperature between about -50° and about 150° C. with a three-component solid catalyst comprising a solid adsorbent in particulate form having a boron trifluoride and water adsorbed thereon. 
     
     
       2. The process for oligomerizing an alpha-olefin in accordance with claim 1 in which a stream of the alpha-olefin is introduced into the reactor and contacted with the said three-component solid catalyst and a product stream is removed from the reactor. 
     
     
       3. The process for oligomerizing an alpha-olefin in accordance with claim 2 in which the solid adsorbent comprises from about 50 to 100 percent silica. 
     
     
       4. The process for oligomerizing an alpha-olefin in accordance with claim 2 in which a partial pressure of boron trifluoride of between about atmospheric and about 1,000 psig. (7.03 MPa) is maintained in the reactor. 
     
     
       5. The process for oligomerizing an alpha-olefin in accordance with claim 2 in which the partial pressure of boron trifluoride in the reactor is between about 50 and about 500 psig. (about 0.44 and about 3.55 MPa). 
     
     
       6. The process for oligomerizing an alpha-olefin in accordance with claim 2 in which the temperature is between about -10° and about 50° C. 
     
     
       7. The process for oligomerizing an alpha-olefin in accordance with claim 2 in which the alpha-olefin comprises 1-decene. 
     
     
       8. The process for oligomerizing an alpha-olefin in accordance with claim 2 in which the water content of the alpha-olefin feed is between about 5 and about 130 ppm. 
     
     
       9. The process for oligomerizing an alpha-olefin in accordance with claim 2 in which the alpha-olefin is flowed through the reactor in contact with a bed of the three-component solid catalyst at a liquid hourly space velocity between about 0.1 and about 50 hour -1 . 
     
     
       10. The process for oligomerizing an alpha-olefin in accordance with claim 2 in which the solid adsorbent has a particle size between about 10 and about 50 mesh (about 0.3 and about 2.0 mm.). 
     
     
       11. The process for oligomerizing 1-decene to a product predominant in the trimer of 1-decene which comprises contacting a stream of 1-decene containing from about 5 to about 130 ppm. water and a stream of boron trifluoride with a catalyst comprising particulate silica at a temperature of between about -10° and about 50° C. under a partial pressure of boron trifluoride between about 10 and about 500 psig. (about 0.17 and about 3.55 MPa). 
     
     
       12. A method of regenerating a deactivated solid catalyst comprising boron trifluoride adsorbed on a solid adsorbent which has been deactivated in the oligomerization of an alpha-olefin, the step which comprises contacting said deactivated solid catalyst with a stream comprising a liquid alpha-olefin containing dissolved water. 
     
     
       13. A method of regenerating a deactivated solid catalyst comprising boron trifluoride adsorbed on a solid adsorbent in accordance with claim 12 in which the solid adsorbent is silica.